Insecticidal composition



Patented Aug. 27, 1940 PATENT OFFICE I 2,212,536 msnc'rromsn COMPOSITION Edgar 0. Britton, Geral W. Zemba, Midland,

d H. Coleman, and John Mich., assignors to The Dow Chemical Company, corporation of Michigan Midland, Mich, a

No Drawing. Application August 24, 193e, Serial No. 291,732;

9 Claims. (UL 167-30) This invention concerns insecticidal spray compositions particularly adapted for combating flies, mosquitoes, and similar insects.

Extracts of such insecticidal plant products as d pyrethrum flowers, derris, cub, timbo, barbasco, and the like .are widely used for the control of insect pests. These toxicants are generally employed in petroleum distillate sprays or in water dispersions. Pyrethrin-containing sprays have a 10 quick paralyzing action on flies and the like, but give a relatively low kill as compared to the per cent knockdown. With rotenone-containing compositions a high moribund kill is generally obtained, although a considerable period of time is requir d to destroy insect pests. The plant extracts generally are unstable to heat and light and lose their efiectiveness to a considerable degree upon storage.

We have discovered that aryloxy-polyalkylene plant products in spray compositions. Solutions of such synthetic ether compounds compare favorably in toxic effect with the plant extracts and have the added advantage of being substantially colorless and odorless and more stable to heat, light, and air than are pyrethrin and rotenon Furthermore, small amounts of these ethers may be added to 'solutions and dispersions of insecticidal plant products containing such toxic principles as pyrethrin and rotenone to obtain improved fly spray compositions which are more stable to heat and light and have a. greater paralyzing efi'ect and greater as tract-containing compositions. By employing these synthetic ether compounds to fortify such known ethercompositions, economies are efiectfortifying common spray compositions comprisinc pyrethrin or rotenone, the ether compound is preferably employed in amount of from about 0.5 to 5 grams per milliliters of the spray soluspecific gravities.

examples The ethers we have found valuable as insecticidal toxicants and stabilizers in spray compositions are those having the following formula:

R(OCnH2n)n-I wherein R represents an aromatic radical and n is an integer from 2 "to 5, inclusive. These compounds are for the most part water-insoluble, substantially odorless, viscous liquids having high Some of the compounds tend m to crystallize on standing. Solutions thereof are substantially non-irritating in the concentrations employed, and do not appear to cause dermatitis on contact with the skin.

The aryloxy-polyalkylene ether iodides are pre-'- 15 pared by reacting sodium iodidewith the corresponding aryloxy-polyalkylene ether chlorides. In carrying out this reaction substantially equimolecular proportions of sodium iodideand the ether chloride are mixed together in an organic solvent, such as; methyl-ethyl ketone, and the reaction mixture thereafter heated to a refluxing temperature for a period of time sufiicient to accomplish the reaction. Sodium chloride is formed as a lay-product and may be removed by washing the mixture with water. The resulting solution of aryloxy-polyalkylene ether iodide is fractionally distilled, whereby the desired ether iodide derivative is obtained in substantially pure form. The preparation and properties of a number of the chloro-ether compounds from-which the corresponding iodo derivatives are prepared are described in co-pending applications, Serial Nos. 225,414, 225,415, and 225,416, filed August 17, 1938, andSerial No. 287,624, filed July 31, 1939.

The method employed in determining the inecticidal toxicltyoi' the spray compositions comprising the above compounds is substantially that 137 F. The invention is illustrated by the following Example 1 2.5 grams of beta-(4-chloro-phcnoxy) -beta'- (2-iodo-ethoxy)-dlethyl ether (boiling at C. at 2 millimeters pressure and having a specific gravity of 1.549 at 20/ C.) was dissolved in 100 milliliters ot the petroleum distillate 55 as employed in the control solution.- This solution was thereafter employed as a spray composition against three-day old houseflies according to the Feet-Grady method and found to give a knockdown of 98 per cent in 10.minutes. In a comparative determination employing the control solution, 100 per cent of the flies were knocked down in 10 minutes. The solution comprising the iodo-ether compound did not show decomposition or deterioration on exposure to air and light, and when sprayed in the testing chamber was substantially non-irritating to the nose and eyes.

Example 2' In a similar manner, tests were carried out with spray compositions comprising other aryloxy-polyalkylene sitions were found to give satisfactory knock- (boiling at PIT-179 C. at

downs and kills, to be stable, and to be substantially non-irritating to humans. For example, 2.5 grams of beta- (2-cyclohexyl-phenoxy) --beta'- iodo-diethyl ether (boiling at l80-l85 G. at 2 millimeters pressure and having a specific gravity of 1.351 at 20l4 C.) was dissolved in the petroleum distillate describedin the preceding example and found to give a knockdown of 72 per cent in 10 minutes and a kill of 40 per cent in 48 hours according to the Feet-Grady method. A more concentrated solution of the same compound containing approximately 3.5 grams per 100 milliliters gave a knockdown of 38 per cent and a kill of 65 per cent in 48 hours. Beta- (i-chloro-phenoxy) -beta'-iodo-diethyl e t h e r and having a specific gravity of 1.627 at 2Ql4 C.) and beta-phenoxy-beta-iodo-diethyl ether (boiling at 160-162 C. at 6 millimeters pressure and having the specific gravity of 1.563 at 20/4 C.) were similarly tested at 2.5 grams per 109 milliliters of spray give knockdowns of 90 and 98 per cent and kills of 50 and 53 per cent in 48 hours, respectively.

Example 3 Mothprooflng tests were carried out with solutions of the aryloxy-polyalkylene ether iodides to determine their of the black carpet in various organic solvents efliciency against the larvae beetle (Attagenus Piceus). This insect and its larvae attack woolens, furs, .and other materials, and are particularly destructive to fabricsused in upholstered furniture, carpets, and rugs. A representative result was obtained with beta- (2,4,6 trichioro phenoxy) beta iodo diethyl ether (boiling at 182-1B3 C. at 2 millimeters pressure and having a specific gravity of 1.739 at 20l4 -C.-). A number of samples of white wool cloth were saturated with a 3 per cent solution of this compound in methyl-ethyl ketone, thereafter pressed to remove excess treating solution, and dried. On each of a number of these samples, five larvae of the black carpet beetle were placed and the sample folded over the larvae. These infested cloth samples were placed in a closed cardboard box and examined from time to time to determine the amount of feeding or other attack directly attributable to the beetle larvae. similar tests were simultaneously carried out on untreated samples of the woolen cloth, both control andtest samples being incubated after infestation at temperatures of F. and at a relative humidity of '10-'15 per cent. Emmination of incubated samples impregnated with the ether iodide solution showed that after 3 weeks there had been no feeding ether iodides. These compo- 2 millimeters pressuresolution and found to of pyrethrum showed heavy feeding throughout the incubation period with a per cent survival of the test larvae. Tests carried out over the sameperiod upon cloth impregnated with methyl-ethyl ketone alone showed feeding by the larvae throughout the incubation period. The material treated with the stained by the initial treatment, had no odor attributable to the toxicant, and showed no tendency' to develop discoloration on standing over an extended period of time.

Other aryloxy-ether iodides may be .substituted for those shown in the examples. The compounds which are so adapted may be classified in subgeneric groups as follows:

a-o-0,.H,..-oc,.Hl.-I a-o-o..H,..-0-o.11i.-o o.m.-I R-0C,.Hi,.0C,.Hi,.0 |-Hh-0- Ear B--OCnH2n0CH2n'0- H:0- H:0- H:I In the foregoing formulas, the group -O-C;Hznmay represent such oxy-alkylene radicals as --OCH2CH:- 00H:CH:-GH:-

CH3 -o-J:n-cmcm -o--cmtn- -O-CH3CHr-CH: CH:

cm -o-.:H-oH,-crn- I 02H: -o- JH-oni CH: CH: -o-tn 11- -O-$-'CH:-

03H! -o-cn,- :n-

sHir- The aryl group R represents cals as those derived from phenol, naphthol, tetrahydro-naphthol, and nuclear substitution products thereof containing one or morephenyl, chlorophenyl, methylphenyl, cyclopentyl, cyclohexyl, methyl-cyclohexyl, methyl, isopropyl, tertiarybutyl, tertiaryamyl, normal-hexyl, tertiaryoxy, tertiary-butoxy, carbethoxy, mine, iodine, andnitro radicals, or the like. These substituents may be attached to the aro matic nucleus in the ortho-, meta-, orparaposition with respect to the hydroxyl grouping.

Likewise, the aryl'oxy-polyalkylene ether iodides may be employed to fortify and stabilize extracts flowers, derris, cu timbo, barbasco, and the like. Besides petro eum distillates, other organic solvents, such as benzen ethylene chloride, hydrogenated naphthalene, butyl alcohol, ketones, etc.,.may be employed. The phrase non-corrosive organic solvent" as employed in the following claims refers to any organic solvent material unreactivewith, and capable of, dissolving the toxicants described, and non-injurious to the skin and general health of humans.

In certain instances it may be desirable to emtoxlcants in ploy the aryloxy ether iodides as such aromatier'adimothprooflng solution was not 1 the principal toxic emulsions or as simplewater dispersions along with soap or other wetting, emulsifying, or detergent. agents and water. Various perfumes or coloring agents may also be incorporated into such compositions where required.

Other modes of applying the principle of our invention may be employed instead of those explained, change being made as regards the mate- 'rials or the amounts thereof employed, provided the compositions defined by any of the following claims or their equivalent be employed.

We therefore particularly point out and distinctly claim asour invention:

1 A liquid insecticidal composition'having dispersed therein as an active'toxicant an aryloxypolyalkylene ether iodide having the formula wherein R represents an aromatic radical and n is an integer from 2 to 5, inclusive.

2. An insecticidal spray comprising a non-corrosive organic solvent having dissolved therein-as ingredient an aryloxy-polyalkylene ether iodide having the formula wherein R represents an aromatic radical and n is an integer from 2to 5, inclusive.

3. A substantially water-free household spray composition comprising a petroleum distillate solvent having dissolved therein as an active toxicant an aryloxy-polyalkylene ether iodide having the formula R( -0153) n-I wherein R represents an aromatic radical and n is an integer from 2 to 5, inclusive.

4. A liquid persed therein as an active toxicant an aryloxy ether iodide having the formula 40 is an integer a o L. I

wherein R represents an aromatic radical and n from 2 to 5, inclusive.

insecticidal composition having d.is-

5. An insecticidal spray comprising a non-corrosive organic solvent having dissolved ,therein as the principal toxic ingredient a compound having theformula R-O -CM-I wherein R represents an aromatic radical, and n is an integer from 2 m5, inclusive.

6. A substantially water-free household spray composition comprising a petroleum distillate solvent having dissolved therein as an active toxicant an aryloxy-polyalkylene ether iodide having the formula R. 0C1LH2 ocnH2 ,I wherein R represents an is an integer from 2 to 5; inclusive.

7. A liquid insecticidal composition having dispersed therein as an active toxicant an aryloxy ether iodide having the formula wherein R represents an aromatic radical.

8. An insecticidal spray comprisinga non-corrosive organic solvent having dissolved therein as the principal toxic ingredient a compound hav- WECMCHZCHZ-I I wherein R represents an aromatic radical. I

aromatic radical and 12 therein as an active toxi- 

